CN102969217B - Thermal desorption ionization device, mass spectrometry system and mass spectrometry method - Google Patents
Thermal desorption ionization device, mass spectrometry system and mass spectrometry method Download PDFInfo
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Abstract
A thermal desorption ionization device is used for desorbing an object to be detected and moving the object to be detected towards an inlet of a mass spectrometer for mass spectrometry. The probe of the sampling unit is used for directly scraping or attaching the analyte of the solid and the liquid, the analyte on the probe is instantly gasified when the probe passes through the channel of the heating unit, and the probe is matched with the charge generation unit to carry out ionization and mass spectrometry, so that the analysis time of the analyte can be greatly shortened. The invention also provides a mass spectrum system comprising the thermal desorption ionization device and a mass spectrum analysis method using the mass spectrum system.
Description
Technical field
The present invention relates to a kind of free device, particularly relate to a kind of thermal desorption and to dissociate device.The present invention also has and includes this thermal desorption about one and to dissociate the mass spectrometer system of device and a mass spectrometric analysis method.
Background technology
By analytical technique of mass spectrum, people can know the molecular weight of determinand (analytes) in a sample, then coordinate further comparison and confirm the true identity of this determinand, therefore since early in the twentieth century development, in order to implement the mass spectrometer of this analytical technique of mass spectrum, because have easy and simple to handle and the advantage of detecting result can be obtained fast, become the Identification Tools of widely each field use already.
Applicant in 1997 with gas chromatograph (gas chromatograph, GC) the multichannel EFI connecting seven tubular types spills the ester mixture of free device to seven kinds of tool different molecular weights and is separated and detects, correlation technique can consult following paper: C.S.Wang, J.Shiea J.MassSpectrom.1997; 32:247..
To spill free method analysing protein composition with EFI, need first by the protein extraction in a histotomy out and obtain a protein solution, the mass spectrometer 1 (hereinafter referred to as ESI-MS) relended by shownschematically comprising an EFI just like Fig. 1 and spill free source 11 carries out protein analysis.Correlation technique can consult following paper: Yamashita, M., Fenn, J.B.J.Phys.Chem.1984; 88,4451., Fenn, J.B.et al.Science 1989; 246,64., Fenn, J.B.etal.Mass Spectrom.Rev.1990; 9,37..
It is spill free (electrospary ionization, ESI) program by protein freeization for carrying out an EFI that the EFI of this mass spectrometer 1 spills free source 11.This free source 11 includes the capillary 112 of an openend 111 towards the entrance 121 of mass analyzer 12, need set up an electric field, such as, form the voltage difference of 2-5kV in this between the two during use between this openend 111 and entrance 121.Afterwards, protein solution to be measured is flowed towards this openend 111 in this capillary 112, solution in this openend 111 can because of the effect of the traction of electric field and fluid level gauge surface tension, and form the taylor cone (Taylor cone) 2 that is abound with electric charge, when electric field action power can overcome the surface tension of liquid, with multivalence electric charge and the drop including protein molecule will be formed, and to spray towards this mass analyzer 12, then enter mass analyzer 12 by this entrance 121.
Consult Fig. 2, then that one utilizes desorption EFI to spill free mass spectrometer (DESI-MS) 3 to spill free method (Desorption electrospray ionization to carry out desorption EFI, and carry out mass spectral analysis DESI), the method can detect molecular weight ranges and multiple compounds widely, also directly can carry out the mass spectrum detecting of protein to a histotomy be moved 4.
This desorption EFI spills the desorption EFI that free mass spectrometer 3 comprises and spills free source 31, EFI shown in similar Fig. 1 spills free source 11, difference is that to spill free source 31 be arrange toward the orientation of this histotomy 4 with one to this desorption EFI, and has more one and surround this capillary 112 and can spray the air-flow delivery member 312 of high pressure draught 311.It is an EFI is spilt medium 32 to pour into this capillary 112 and impose high voltage and spill program to carry out above-mentioned EFI that this desorption EFI spills free source 31, plural charged drop 321 and high pressure draught 311 can be sprayed in the same way from this openend 111 during startup, and clash into a histotomy 4 by high pressure draught 311, make the determinand in this histotomy 4 stressed and desorption, with charged drop 321 in conjunction with charged and form ionic state, then can be received by the entrance 33 of mass analyzer again and carry out follow-up mass spectral analysis by the determinand of desorption.
But high pressure draught 311 is not easily concentrated after being ejected, be difficult to the region precisely controlled for clashing into, the protein space analysis of precision cannot be carried out to this histotomy 4, separately, bombard the desorption energy of this histotomy 4 with charged drop 321, be not sufficient to the protein molecule that desorption efficiently goes out to be tied to.
2002, applicant reintroduces fusion drop EFI and spills free method (Fused DropletElectrospray Ionization, or be called second order segmentation EFI and spill free method (Two-Step Electrospray Ionization) and various free method developed subsequently FD-ESI).Be different from general EFI and spill free mass spectrography, second order segmentation EFI spill free method be by analyte after pre-treatment, directly push via the high-tension capillary of applying one with pump, and spill free analyte at end generation EFI, its way is first utilized by analyte solution atomizer (ultrasonic atomizer or pressurized nebulizer etc.) to make it be atomized to produce size about between the fine droplet of 10-30 μm, these fine droplets generate charged analyte ions spilling produced charged droplets fusion reaction with EFI, EFI now spills the design of free source, become single capillary from multichannel to carry out EFI and spill, and become the Main Basis of follow-up free source design, correlation technique can consult following paper: D.Y.Chang, C.C.Lee, J.Shiea, Anal.Chem.2002, 74, 2465., C.C.Lee, D.Y.Chang, J.Y.Jeng, J.Shiea, J.Mass Spectrom.2002,37,115..
Technology (the Electrospray-Assisted Pyrolysis Mass Spectrometry spilling free auxiliary heat Pyrolysis Mass Spectrometry with EFI is developed again in applicant in 2005, ESA-Py/MS), be used for analyzing large molecule (macromolecular), comprise the species Rapid identification that the synthesis macromolecule of tool solubility and insolubility and natural high molecular substance comprise the rapid analysis of crude oil, amber and humus, correlation technique can consult following paper: H.J.Hsu, T.L.Kuo, S.H.Wu, J.N.Oung, J.Shiea, Anal.Chem.2005,77,7744.; H.J.Hsu, J.N.Oung, T.L.Kuo, S.H.Wu, J.Shiea, Rapid Commun.Mass Spectrom.2007.21,375..
But above-mentioned experimental provision volume is all too huge, quite takes up room.In addition, sample feeding is quite loaded down with trivial details, need first sample to be sent into high temperature furnace and be heated to design temperature formation gaseous state, pass into again current-carrying gas mix with gaseous sample after through guiding to free region by conduit, not only operate inconvenience consuming time again, and can duct wall be residued in and cause sample size loss in the process of sample transmission.
Summary of the invention
The first object of the present invention, is namely to provide the thermal desorption of a kind of fast sampling and analysis to dissociate device.
Thermal desorption of the present invention dissociates device, for a kind of determinand is carried out desorption, and move to carry out mass spectral analysis towards a mass spectrometric entrance, this thermal desorption device that dissociates comprises an electric charge generation unit, a heating unit, and a sampling unit.
This electric charge generation unit is and this mass spectrometer interval is arranged and produce charged solvent droplets towards this mass spectrometric entrance.This heating unit comprises a heater body, and a passage running through this heater body, this passage has an injection port, and an outlet in contrast to this injection port, this outlet is towards between this electric charge generation unit and mass spectrometer, and the bearing of trend of this outlet is crossing with the bearing of trend of this electric charge generation unit.This sampling unit comprises the probe that can be extended through the passage of this heating unit with detaching, and this probe is in order to scraping or attaches this determinand, and part determinand is attached on this probe.
Thermal desorption of the present invention dissociates device, wherein, this sampling unit also comprises the grip part that is connected to this probe one end, and this grip part has one and connects this probe and towards the joint face of this injection port, the area of this joint face is the cross section being greater than this injection port.
Thermal desorption of the present invention dissociates device, wherein, this electric charge generation unit is that the mode of spraying produces charged solvent droplets, and the mode of spraying is selected from one of following method: EFI spills free method, nanometer sprays free method, ullrasonic spraying dissociates method, and heat sprays free method.
Thermal desorption of the present invention dissociates device, and wherein, this electric charge generation unit is that the mode of discharging produces charged solvent droplets, and the mode of electric discharge is selected from one of following method: point discharge, glow discharge, and dielectric barrier discharge.
Thermal desorption of the present invention dissociates device, and wherein, the heating temperature range of the heater body of this heating unit is 40 ~ 1500 DEG C.
Second object of the present invention, is namely providing a kind of mass spectrometer system, comprises the mass spectrometer that has an entrance, and the thermal desorption described in the present invention first object dissociates device.
Mass spectrometer system of the present invention, wherein, this sampling unit also comprises the grip part that is connected to this probe one end, and this grip part has one and connects this probe and towards the joint face of this injection port, the area of this joint face is the cross section being greater than this injection port.
Mass spectrometer system of the present invention, wherein, this electric charge generation unit is that the mode of spraying produces charged solvent droplets, and the mode of spraying is selected from one of following method: EFI spills free method, nanometer sprays free method, ullrasonic spraying dissociates method, and heat sprays free method.
Mass spectrometer system of the present invention, wherein, this electric charge generation unit is that the mode of discharging produces charged solvent droplets, and the mode of electric discharge is selected from one of following method: point discharge, glow discharge, and dielectric barrier discharge.
Mass spectrometer system of the present invention, wherein, the heating temperature range of the heater body of this heating unit is 40 ~ 1500 DEG C.
3rd object of the present invention, then providing a kind of mass spectrometric analysis method, comprises a sampling procedure, desorption, an electric charge generating step, and an analytical procedure.
This sampling procedure is with a probe scraping or attaches a kind of determinand, makes part determinand be attached on this probe; This desorption this probe is stretched into one run through in the passage of a heater body, and make the determinand on this probe be added thermal desorption by this heater body to form gas phase determinand and leave this passage again; This electric charge generating step makes an electric charge generation unit produce charged solvent droplets towards a mass spectrometric entrance, and gas phase determinand can merge with solvent droplets and forms charged determinand ion; This analytical procedure makes determinand ion enter this mass spectrometer via this entrance, and analyze through this mass spectrometer.
Mass spectrometric analysis method of the present invention, wherein, the heating temperature range of the heater body of this heating unit is 40 ~ 1500 DEG C.
Beneficial effect of the present invention is: utilize the direct scraping of this probe or attach the analysans of solid and liquid, and make this probe by the analysans transient evaporation on probe being carried out during passage free and mass spectral analysis, significantly can shorten the analysis time of analysans.
Accompanying drawing explanation
Fig. 1 is a schematic diagram, illustrates that prior art one EFI spills relative position and the type of action of each large parts of free mass spectrometer (ESI-MS);
Fig. 2 is a schematic diagram, illustrates that prior art one desorption EFI spills relative position and the type of action of each large parts of free mass spectrometer (DESI-MS);
Fig. 3 is a schematic diagram, and the preferred embodiment of mass spectrometer system of the present invention is described;
Fig. 4 is a flow chart, and the preferred embodiment of mass spectrometric analysis method of the present invention is described;
Fig. 5 ~ 16 are all Selective ion mode tomographic map and mass spectrogram, for illustration of the analysis result of each experimental example of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.
Consulting Fig. 3, is the preferred embodiment of mass spectrometer system 5 of the present invention, comprises the mass spectrometer 6 that has an entrance 61, and a thermal desorption dissociates device 7.For having in this technical field, the structure of this mass spectrometer 6 knows that the knowledgeable can understand usually, repeat no more, and this thermal desorption dissociates, device 7 comprises electric charge generation unit 71, heating unit 72, and a sampling unit 73.
This electric charge generation unit 71 is and this mass spectrometer 6 interval is arranged and entrance 61 towards this mass spectrometer 6 produces charged solvent droplets.Be noted that, in the present embodiment, this electric charge generation unit is that the mode of spraying produces charged solvent droplets, and the mode of spraying can be selected from one of following method: EFI spills free method (electrospray ionization), nanometer sprays free method (Nanospray), ullrasonic spraying dissociates method (Sonic spray), and heat sprays free method (Thermal spray).In addition, this electric charge generation unit also can produce charged solvent droplets in the mode of electric discharge, and the mode of electric discharge is selected from one of following method: point discharge (corona discharge), glow discharge (glow discharge), and dielectric barrier discharge (dielectricbarrier discharge).
This heating unit 72 comprises a heater body 721, and the passage 722 that runs through this heater body 721, the heating temperature range of this heater body 721 is 40 ~ 1500 DEG C, this passage 722 has an injection port 723, and one in contrast to the outlet 724 of this injection port 723, this outlet 724 is towards between this electric charge generation unit 71 and mass spectrometer 6, and the bearing of trend of this outlet 724 is crossing with the bearing of trend of this electric charge generation unit 71.
This sampling unit 73 comprises the probe 731 that can be extended through the passage 722 of this heating unit 72 with detaching, and the grip part 732 that is connected to this probe 731 one end.This probe 731 is in order to scraping or the determinand (not shown) attaching a solid or liquid, part determinand is made to be attached on this probe 731, this grip part 732 has this probe 731 of a connection and towards the joint face 733 of this injection port 723, the area of this joint face 733 is the cross sections being greater than this injection port 723.
Consult Fig. 4, for the preferred embodiment of mass spectrometric analysis method of the present invention, it coordinates aforementioned mass spectrometer system 5 with the method for being carried out analyzing by analysans, comprise sampling procedure 81, desorption 82, electric charge generating step 83, and an analytical procedure 84, below coordinate Fig. 3,4 that the step of carrying out mass spectrometric analysis method with this mass spectrometer system 5 is described.
This sampling procedure 81 is with this probe 731 scraping or attaches determinand, makes part determinand be attached on this probe 731; This desorption 82 is stretched in this passage 722 by this injection port 723 by this probe 731, and make the determinand on this probe 731 be added thermal desorption by this heater body 721 to form gas phase determinand and leave this passage 722 by this outlet 724 again.Operator can adjust the heating-up temperature of this heater body 721 according to determinand of different nature, leave this passage 722 to guarantee determinand can be heated to formation gas phase.The design of this grip part 732, operator not only can be allowed to be easy to operation, and the area of the joint face 733 of this grip part 732 is the cross sections being greater than this injection port 723, wholely when this probe 731 can be avoided to stretch in this passage 722 falls in this passage 722.
This electric charge generating step 83 makes this electric charge generation unit 71 produce charged solvent droplets towards the entrance 61 of this mass spectrometer 6, and gas phase determinand can merge with solvent droplets and forms charged determinand ion, the method of the solvent droplets of generating strap electric charge as previously mentioned, repeats no more in this; This analytical procedure 84 makes determinand ion enter this mass spectrometer 6 via this entrance 61, and produce a mass spectral analysis figure after this mass spectrometer 6 is analyzed.
What illustrate is, in the present embodiment, the heating temperature range of this heater body 721 is 40 ~ 800 DEG C, this temperature range is only the operating condition that the present embodiment is illustrated, can certainly be heated to depending on real-life operational situation more than 800 DEG C, even reach about 1500 DEG C, be not limited with person disclosed by the present embodiment.
Fig. 5 to Figure 13 carries out with the device and method of the present invention the experimental example tested, all with the mass spectrometer system 5 shown in Fig. 3, and the analytical procedure shown in Fig. 4 is tested, each figure all shows Selective ion mode tomographic map and mass spectrogram, dependency structure and step as previously mentioned, repeat no more in following explanation.
As shown in Figure 5,6, be to test after probe 731 respectively scraping Acetaminophen lozenge and rhythm of the heart ingot surface, and by Fig. 5,6 result, proved invention really can Direct Analysis solid sample composition, and detects the active component contained by solid sample.
As shown in Figure 7,8, be that head-shaking pill powder and heroin powder are mixed in respectively in commercially available flour and are modeled to drug powder, this probe 731 attached above-mentioned mixed powder respectively and tests.By Fig. 7,8 result, really can detect the existence of head-shaking pill and heroin, proved invention really can the composition of Direct Analysis powdered samples.
As shown in Fig. 9,10, be add KET respectively in urine, and add melamine in milk, this probe 731 is attached above-mentioned mixed liquid respectively and tests.By Fig. 9,10 result, really can detect the existence of KET and melamine, proved invention really can the composition of Direct Analysis fluid sample.
As shown in Figure 11 ~ 13, be difference test day staple, as toy, enema bag, and in erasing rubber, whether contain the composition of plasticiser.To test after probe 731 respectively scraping or the above-mentioned article surface that punctures, and by the result of Figure 11 ~ 13, proved invents the plasticiser composition that really can detect in solid sample.
As shown in Figure 14 ~ 16, be respectively for the test of vegetables and fruits surface of agricultural products residues of pesticides, Figure 14 ~ 16 are with probe 731 respectively scraping green pepper, tomato and wax-apple surface, and test analysis whether remains of pesticide.By the result of Figure 14 ~ 16, proved invention can detect the residual agricultural chemicals of surface of agricultural products really.
In sum, the present invention is by above-mentioned device and method, utilize this probe 731 directly scraping or attach the analysans of solid and liquid, and when making this probe 731 by passage 722, the heat effect of this heater body 721 can be subject to, make the analysans transient evaporation on this probe 731 and carry out free and mass spectral analysis, not only can obtain assay (on average about 3-5 can produce assay second) fast, and the replacing of analysans and sampling all quite quick, significantly can shorten the analysis time of analysans, and the detection of a large amount of sample number can be applied to, and analysans does not need to carry out pre-treatment, and can operate under normal temperature and pressure conditions, operating performance is easy.
Claims (12)
1. thermal desorption dissociates a device, is for a kind of determinand is carried out desorption, and moves to carry out mass spectral analysis towards a mass spectrometric entrance, it is characterized in that: this thermal desorption device that dissociates comprises:
An electric charge generation unit, and this mass spectrometer interval arranges and produces charged solvent droplets towards this mass spectrometric entrance;
A heating unit, comprise a heater body, and a passage running through this heater body, this passage has an injection port, and an outlet in contrast to this injection port, this outlet is towards between this electric charge generation unit and mass spectrometer, and the bearing of trend of this outlet is crossing with the bearing of trend of this electric charge generation unit; And
A sampling unit, comprise the probe that can be extended through the passage of this heating unit with detaching, this probe is in order to scraping or attaches this determinand, makes part determinand be attached on this probe;
When the determinand on this probe is along with this probe is via the passage of this injection port by this heating unit, and added thermal desorption by this heater body and form gas phase determinand after being left by this outlet, can and this electric charge generation unit solvent droplets that produce merge and form charged determinand ion, and enter this mass spectrometric entrance and analyze.
2. thermal desorption according to claim 1 dissociates device, it is characterized in that: this sampling unit also comprises the grip part that is connected to this probe one end, this grip part has one and connects this probe and towards the joint face of this injection port, the area of this joint face is the cross section being greater than this injection port.
3. thermal desorption according to claim 1 dissociates device, it is characterized in that: this electric charge generation unit is that the mode of spraying produces charged solvent droplets, and the mode of spraying is selected from one of following method: EFI spills free method, nanometer sprays free method, ullrasonic spraying dissociates method, and heat sprays free method.
4. thermal desorption according to claim 1 dissociates device, it is characterized in that: this electric charge generation unit is that the mode of discharging produces charged solvent droplets, and the mode of electric discharge is selected from one of following method: point discharge, glow discharge, and dielectric barrier discharge.
5. thermal desorption according to claim 1 dissociates device, it is characterized in that: the heating temperature range of the heater body of this heating unit is 40 ~ 1500 DEG C.
6. a mass spectrometer system, in order to carry out mass spectral analysis for a kind of determinand, is characterized in that: this mass spectrometer system comprises:
A mass spectrometer, has an entrance, for receiving and analyzing the determinand ion dissociated by desorption; And
A thermal desorption dissociates device, comprising:
An electric charge generation unit, and this mass spectrometer interval arranges and produces charged solvent droplets towards this mass spectrometric entrance;
A heating unit, comprise a heater body, and a passage running through this heater body, this passage has an injection port, and an outlet in contrast to this injection port, this outlet is towards between this electric charge generation unit and mass spectrometer, and the bearing of trend of this outlet is crossing with the bearing of trend of this electric charge generation unit; And
A sampling unit, comprise the probe that can be extended through the passage of this heating unit with detaching, this probe is in order to scraping or attaches this determinand, makes the sample segment molecule attached of this determinand on this probe;
When the determinand on this probe is along with this probe is via the passage of this injection port by this heating unit, and added thermal desorption by this heater body and form gas phase determinand after being left by this outlet, can and this electric charge generation unit solvent droplets that produce merge and form charged determinand ion, and enter this mass spectrometric entrance and analyze.
7. mass spectrometer system according to claim 6, it is characterized in that: this sampling unit also comprises the grip part that is connected to this probe one end, this grip part has one and connects this probe and towards the joint face of this injection port, the area of this joint face is the cross section being greater than this injection port.
8. mass spectrometer system according to claim 6, it is characterized in that: this electric charge generation unit is that the mode of spraying produces charged solvent droplets, and the mode of spraying is selected from one of following method: EFI spills free method, nanometer sprays free method, ullrasonic spraying dissociates method, and heat sprays free method.
9. mass spectrometer system according to claim 6, is characterized in that: this electric charge generation unit is that the mode of discharging produces charged solvent droplets, and the mode of electric discharge is selected from one of following method: point discharge, glow discharge, and dielectric barrier discharge.
10. mass spectrometer system according to claim 6, is characterized in that: the heating temperature range of the heater body of this heating unit is 40 ~ 1500 DEG C.
11. 1 kinds of mass spectrometric analysis methods, is characterized in that: this mass spectrometric analysis method comprises:
A sampling procedure, with a probe scraping or attach a kind of determinand, makes part determinand be attached on this probe;
A desorption, stretches into one by this probe and runs through in the passage of a heater body, and makes the determinand on this probe be added thermal desorption by this heater body to form gas phase determinand and leave this passage again;
An electric charge generating step, makes an electric charge generation unit produce charged solvent droplets towards a mass spectrometric entrance, and gas phase determinand can merge with solvent droplets and forms charged determinand ion; And
An analytical procedure, determinand ion enters this mass spectrometer via this entrance, and analyzes through this mass spectrometer.
12. mass spectrometric analysis methods according to claim 11, is characterized in that: the heating temperature range of this heater body is 40 ~ 1500 DEG C.
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TW100131274A TWI449081B (en) | 2011-08-31 | 2011-08-31 | Thermal desorption ionization device, mass spectrometer, and method for mass spectrometry |
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TWI488216B (en) * | 2013-04-18 | 2015-06-11 | Univ Nat Sun Yat Sen | A ionization device of multi source, for a mass spectrometry analysis system |
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